CN105646755B - A kind of method for improving trans Isosorbide-5-Nitrae polyisoprene rate of polymerization - Google Patents
A kind of method for improving trans Isosorbide-5-Nitrae polyisoprene rate of polymerization Download PDFInfo
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- CN105646755B CN105646755B CN201610046966.8A CN201610046966A CN105646755B CN 105646755 B CN105646755 B CN 105646755B CN 201610046966 A CN201610046966 A CN 201610046966A CN 105646755 B CN105646755 B CN 105646755B
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 21
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 150000003608 titanium Chemical class 0.000 claims abstract description 6
- 229920001887 crystalline plastic Polymers 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000004411 aluminium Substances 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003426 co-catalyst Substances 0.000 claims abstract description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 9
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 230000001603 reducing effect Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 238000012673 precipitation polymerization Methods 0.000 claims description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000010936 titanium Substances 0.000 description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 239000005060 rubber Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 5
- 239000000899 Gutta-Percha Substances 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 4
- 240000000342 Palaquium gutta Species 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920000588 gutta-percha Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910010062 TiCl3 Inorganic materials 0.000 description 2
- 238000010959 commercial synthesis reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000012781 shape memory material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of method for improving trans Isosorbide-5-Nitrae polyisoprene rate of polymerization, using load-type Titanium series catalyst as major catalyst, aluminium agent is co-catalyst, third component is added into catalyst system, is catalyzed isoprene polymerization into the Crystalline plastics with trans Isosorbide-5-Nitrae structure.Third component and catalyst collective effect, improve and are catalyzed trans Isosorbide-5-Nitrae polyisoprene rate of polymerization, reduce the production cycle, reduce cost, there is provided a kind of TPI preparation methods of strong applicability.
Description
Technical field
The present invention relates to synthesis of polymer material rubber materials, and in particular to one kind improves anti-form-1,4- polyisoprene
The method of rubber rate of polymerization.
Background technology
Anti-form-1,4- polyisoprene（TPI）Also known as artificial synthesized gutta-percha, both the strand with unsaturated rubber was soft
It is pliable and can cure characteristics, there is the easy crystallinity of tacticity polymer again, thus can both show thermoplastic property, again
Caoutchouc elasticity volume property can be showed.Double bond in its strand can be vulcanized；The compliance of chain is to may make up the base of elastomer
Plinth；The order of trans configuration makes it easier to crystallize, and this is to cause it and natural rubber（NR）Different deciding factors.TPI
The trans chain link identical period it is short, occur under normal temperature in the form of folded chain, less than 60 DEG C, i.e. rapid crystallization, is with high rigidity
With the Crystalline plastics of high tensile.
TPI can be used as rubber elastomeric material, and the most outstanding feature of TPI vulcanizates is that rolling resistance is small, and heat is low, resistance to tired
Labor and anti-wear performance are good.Research shows that the general purpose rubber such as TPI and NR, SBR, BR of synthesis has blending intervulcanizability energy well,
When the mass fraction of TPI rubbers is 20% -30%, its blend compounds can not only keep every mechanical property of virgin rubber, and it is dynamic
State property can improve significantly（Such as low-heat-generation, low-rolling-resistance, endurance）, it is the preferable material for manufacturing High-performance green tire
Material.In addition, TPI can be additionally used in other a variety of occasions as the substitute of gutta-percha, its main application fields is：1. artificial limb
The medical function materials such as set, sports safety rehabilitation protector and brace；2. thermostimulation shape-memory material, such as special-shaped pipe joint,
Multi-core cable joint, temperature detect switch (TDS) etc.；3. TPI and plastic blend, improve the processing characteristics of plastics.Gutta-percha have it is excellent into
Film, film strength and air-tightness are very outstanding, available for the manufacture saturating radar wave encapsulant of air-tightness；4. golf coats
Layer, insulating material, submarine cable etc..
The catalyst system of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene mainly has vanadium system, vanadium/titanium mixed system, titanium system.
Vanadium system：The microstructure of most of catalyst system products therefrom is by catalyst proportion, temperature, solvent and additional
The influence of the conditions such as electron donor is all insensitive, but polymerization speed is very slow, and polymer yield is at a fairly low.On its basis
Modified catalyst, although although yield increases, increase rate is little, and contains mixing in obtained polymer
Gel is not decomposed, the shortcomings of crystallinity and fusing point are relatively low.VOCl3/AlR3Obtained polymer is in relative molecular mass and has rule
Lower than other halogenation vanadium on vertical structure, its anti-form-1,4- structural contents only have 90 % or so, it is difficult to prepare highly crystalline TPI.
Vanadium/titanium mixed system：This is a kind of improved catalysts that high trans structure TPI can be made, and with regard to polymerization speed,
Also all it is higher for polymer yield and trans content.They can be divided into two types：One kind is heterogeneous system, including
VCl3/TiCl3/AlEt3Three mutually mixes, or VCl3With AlEt3The system being deposited on together on titanium trichloride；Another kind is can
Dissolubility system, it is made up of alkoxytitanium, trialkylaluminium and a kind of be carried on inert media vanadium trichloride.VCl3/
β-TiCl3/AlEt3Fast 50 times when average polymerization reaction rate caused by catalyst is than being used alone vanadium trichloride.But it is still
Use solution polymerization process.
Titanium system：The Huang Bao treasures seminar of University Of Qingdao of China develops one kind and obtains supported titanium using mechanical lapping and urge
Change the polymerization of isoprene bulk depositing, directly synthesize the new technology of TPI powders, be aggregated in N2Protection is lower to be carried out, according to
Secondary addition isoprene, catalyst, lower stage feeding polymerization are stirred until complete monomer conversion is polymer beads, catalytic efficiency is more than
50 kg condensates/g Ti.With above-mentioned external vanadium system solution polymerization ratio, production technology is greatly simplified, and catalytic efficiency can improve
30 times or so, and energy and material consumption is greatly reduced, basic three-waste free discharge, therefore production cost is not only more much lower than foreign countries production TPI,
Even than general containing intermingle with, method isoprene rubber is also low, is TPI popularization and application, and the application particularly in rubber tyre is created
Condition.
In the prior art, solution polymerization process commercial synthesis anti-form-1, during 4- polyisoprene, due to its catalytic efficiency very
Low, complex process, energy and material consumption height etc., price are higher than more than ten times of General Purpose Rubber, it is difficult to popularization and application.Therefore the present invention is for most
There are the carrying catalyst in titanium series of the market competitiveness, especially MgCl2/TiCl4- triisobutyl aluminium catalyst system proposes increase
The method of its rate of polymerization, and its truly feasible example is given, reduced the production cycle for commercial synthesis gutta-percha, increase production
Amount, reduces cost.
The content of the invention
The present invention is solution the deficiencies in the prior art, there is provided one kind improves anti-form-1,4- polyisoprene rates of polymerization
Method, reduce production cycle and cost.
The present invention is achieved through the following technical solutions：
One kind improves anti-form-1, and the method for 4- polyisoprene rates of polymerization, it is characterized in that：With load-type Titanium series
Catalyst is major catalyst, and aluminium agent is co-catalyst, adds third component into catalyst system, catalysis isoprene polymerization into
With anti-form-1, the Crystalline plastics of 4- structures；The third component is the elemental metals with reducing property.
The raising anti-form-1 of the present invention, the method for 4- polyisoprene rates of polymerization, the simple substance with reducing property
Metal is preferably iron.
The raising anti-form-1 of the present invention, the method for 4- polyisoprene rates of polymerization, the load-type Titanium series catalyst are
MgCl2Load TiCl4Type catalyst MgCl2/ TiCl4, its preparation method is ball-milling method, chemical method, ball milling and chemical combined method
In one kind.
The raising anti-form-1 of the present invention, the method for 4- polyisoprene rates of polymerization, the polymerization methodses of isoprene are this
Body precipitation polymerization, including prepolymerization, polymerization and devolatilization are dried；The pre-polymerization process is being sufficiently stirred lower progress, prepolymerization temperature
Spend for-15-5 DEG C, prepolymerization time 0.5-10h；The polymerization process is being sufficiently stirred lower progress, polymerization process addition chain
Transfer agent, polymerization temperature are 10-35 DEG C, polymerization time 10-40h；The chain-transferring agent is hydrogen, is led to when polymerizeing and starting
Enter, the pressure for being passed through hydrogen is 0.001-1 MPa.
The raising anti-form-1 of the present invention, the method for 4- polyisoprene rates of polymerization, operation are as follows：Anoxybiotic, exhausted water, absolutely
Under conditions of impurity, first two container single port bottles are cleaned, dry, vacuumized, use N2For several times, one of bottle is taken out for displacement
Vacuum, and add isoprene monomer and quantitative AlR3, another bottle adds major catalyst and different types of reproducibility
Fe element simultaneously vacuumizes；By isoprene monomer and AlR3The bottle equipped with major catalyst and iron element is added under stirring
In son, it is being sufficiently stirred lower stage feeding polymerization and is being passed through the hydrogen of certain pressure, is finally being terminated with the ethanol solution equipped with stabilizer
Polymerization；Resulting polymers particle is dried to constant weight in vacuum drying chamber, weighs and calculates conversion ratio, catalytic efficiency, test
Its trans content, Mooney；Polymerizing condition is：Ti/Ip>2.5×10-6(mol ratio, similarly hereinafter), Al/Ti 10-300, fe can
Think iron wire, iron powder, iron block, nanometer iron powder, reproducibility iron powder, and the material containing fe such as magnet.
The beneficial effects of the invention are as follows：The present invention adds the third component metal with reducing property in catalyst system
Simple substance, catalysis anti-form-1 is improved, 4- polyisoprene rates of polymerization, the production cycle is reduced, reduces cost, there is provided one kind is applicable
The strong TPI preparation methods of property.
Embodiment
Embodiment 1
First two 500 ml container single port bottles are cleaned, dry, vacuumized, with pure N2Displacement for several times and numbering 1,2, by 1
Number bottle adds catalyst MgCl2/ TiCl4, rotor and reduced iron powder and vacuumize, No. 2 bottles vacuumize, and add isoamyl two
Alkene monomer and quantitative AlR3, mol ratio Ti/Ip=1.25 × 10 of Ti and isoprene-4, Al and Ti mol ratios Al/Ti=60,
By isoprene monomer and AlR in No. 2 bottles3, No. 1 equipped with catalyst, rotor and reduced iron powder is added under stirring
In bottle, lower stage feeding polymerization is being sufficiently stirred, polymerization time 20 hours, polymerization is being terminated with the ethanol solution equipped with stabilizer.Will
Resulting polymers particle is dried to constant weight in vacuum drying chamber, and isoprene conversion ratio is 28 %, catalytic efficiency 3.246
kg/g Ti。
Comparative example 1
First two 500 ml container single port bottles are cleaned, dry, vacuumized, with pure N2Replace for several times and number, by headpin
Son adds catalyst and rotor and vacuumized, and No. 2 bottles vacuumize, and add isoprene monomer and quantitative AlR3, Ti with
Mol ratio Ti/Ip=1.25 × 10 of isoprene-4, Al and Ti mol ratios Al/Ti=60, by isoprene monomer in No. 2 bottles and
AlR3, it is added under stirring in headpin equipped with catalyst and rotor, is being sufficiently stirred lower stage feeding polymerization, is polymerize
20 hours time, polymerization is terminated with the ethanol solution equipped with stabilizer.Resulting polymers particle is dried in vacuum drying chamber
To constant weight, isoprene conversion ratio is 2.201 %, and catalytic efficiency is 255 g/g Ti.
Embodiment 2
First two 500 ml container single port bottles are cleaned, dry, vacuumized, with pure N2Replace for several times and number, by headpin
Son adds catalyst, rotor and thin wire simultaneously vacuumize, and No. 2 bottles vacuumize, and adds isoprene monomer and quantitative
AlR3, mol ratio Ti/Ip=1.25 × 10 of Ti and isoprene-4, Al and Ti mol ratios Al/Ti=150, by isoamyl in No. 2 bottles
Diene monomers and AlR3, it is added under stirring in headpin equipped with catalyst, rotor and thin wire, is fully stirring
Lower stage feeding polymerization is mixed, polymerization time 20 hours, polymerization is terminated with the ethanol solution equipped with stabilizer.Resulting polymers particle is existed
It is 168.7 to be dried in vacuum drying chamber to constant weight, test Mooney.
Comparative example 2
First two 500 ml container single port bottles are cleaned, dry, vacuumized, with pure N2Replace for several times and number, by headpin
Son adds catalyst and rotor and vacuumized, and No. 2 bottles vacuumize, and add isoprene monomer and quantitative AlR3, Ti with
Mol ratio Ti/Ip=1.25 × 10 of isoprene-4, Al and Ti mol ratios Al/Ti=150, by isoprene monomer in No. 2 bottles and
AlR3, add and be equipped with catalyst and rotor headpin under stirring, be sufficiently stirred lower stage feeding polymerization, polymerization time
20 hours, polymerization is terminated with the ethanol solution equipped with stabilizer.Resulting polymers particle is dried to perseverance in vacuum drying chamber
Weight, test Mooney are 152.6.
Embodiment 3
First two 500 ml container single port bottles are cleaned, dry, vacuumized, with pure N2Replace for several times and number, by headpin
Son adds catalyst, rotor and thin wire simultaneously vacuumize, and No. 2 bottles vacuumize, and adds isoprene monomer and quantitative
AlR3, mol ratio Ti/Ip=1.25 × 10 of Ti and isoprene-4, Al and Ti mol ratios Al/Ti=120, by isoamyl in No. 2 bottles
Diene monomers and AlR3, it is added under stirring in headpin equipped with catalyst, rotor and thin wire, is fully stirring
Lower stage feeding polymerization is mixed, polymerization time 20 hours, polymerization is terminated with the ethanol solution equipped with stabilizer.Resulting polymers particle is existed
It is 152.8 to be dried in vacuum drying chamber to constant weight, test Mooney.
Claims (5)
1. one kind improves anti-form-1, the method for 4- polyisoprene rates of polymerization, it is characterised in that：With load-type Titanium series catalyst
For major catalyst, aluminium agent is co-catalyst, third component is added into catalyst system, catalysis isoprene polymerization is into anti-
The Crystalline plastics of formula-Isosorbide-5-Nitrae-structure；The third component is the fe with reducing property.
2. raising anti-form-1 according to claim 1, the method for 4- polyisoprene rates of polymerization, it is characterised in that：Institute
It is MgCl to state load-type Titanium series catalyst2Load TiCl4Type catalyst MgCl2/ TiCl4, its preparation method is ball-milling method, chemistry
One kind in method, ball milling and chemical combined method.
3. raising anti-form-1 according to claim 1, the method for 4- polyisoprene rates of polymerization, it is characterised in that：It is different
The polymerization methodses of pentadiene are bulk precipitation polymerization, including prepolymerization, polymerization and devolatilization are dried.
4. raising anti-form-1 according to claim 3, the method for 4- polyisoprene rates of polymerization, it is characterised in that：Institute
It is-15-5 DEG C that pre-polymerization process, which is stated, being sufficiently stirred lower progress, prepolymerization temperature, prepolymerization time 0.5-10h；It is described poly-
Conjunction process is being sufficiently stirred lower progress, and polymerization process addition chain-transferring agent, polymerization temperature is 10-35 DEG C, polymerization time 10-
40h。
5. raising anti-form-1 according to claim 4, the method for 4- polyisoprene rates of polymerization, it is characterised in that：Institute
It is hydrogen to state chain-transferring agent, is passed through when polymerizeing and starting, the pressure for being passed through hydrogen is 0.001-1 MPa.
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| CN201610046966.8A CN105646755B (en) | 2016-01-25 | 2016-01-25 | A kind of method for improving trans Isosorbide-5-Nitrae polyisoprene rate of polymerization |
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| CN105646755B true CN105646755B (en) | 2018-03-27 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB840165A (en) * | 1958-04-28 | 1960-07-06 | Goodyear Tire & Rubber | Method of preparing 1,4 trans polyisoprene |
| CN1425699A (en) * | 2001-12-12 | 2003-06-25 | 黄宝琛 | Synthesis of medium and low relative molecular mass trans-1,4-polyisoprene wax and trans-1,4-poly butadiene wax |
| CN1847272A (en) * | 2006-04-11 | 2006-10-18 | 青岛科大方泰材料工程有限公司 | Industrial synthesis process of high trans-1, 4-iroprene polymer |
-
2016
- 2016-01-25 CN CN201610046966.8A patent/CN105646755B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB840165A (en) * | 1958-04-28 | 1960-07-06 | Goodyear Tire & Rubber | Method of preparing 1,4 trans polyisoprene |
| CN1425699A (en) * | 2001-12-12 | 2003-06-25 | 黄宝琛 | Synthesis of medium and low relative molecular mass trans-1,4-polyisoprene wax and trans-1,4-poly butadiene wax |
| CN1847272A (en) * | 2006-04-11 | 2006-10-18 | 青岛科大方泰材料工程有限公司 | Industrial synthesis process of high trans-1, 4-iroprene polymer |
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